Preparation of aviation gasoline from normally gaseous hydrocarbons



P. MILLER April 23, 1946.

PREPARATION OF AVIATION GASOLINE FROM NORMALLY GASEOUS HYDROCARBONS Filed Feb. 1o, 1942 Patented Apr. 23, 1946 PREPARATION OF AVIATION GASOLINE FROM NORMALLY GASEOUS HYDROCAR- BONS Pharis Miller, Elizabeth, N. 1 assigner, by mesne assignments, to Standard Catalytic Company, a corporation of Delaware Application February 1o, 1942, sensi No. 430,19@

4 claims. (cieco-csail 'I'his invention relates to the preparation of liquid aviation gasoline hydrocarbons from a variety of normally gaseous hydrocarbons, particularly to obtain a fuel which gives excellent performance in` supercharged aircraft engines of high-power output.

While a number of processes have been developed for polymerizing and alkylating certain normally gaseous hydrocarbons to form liquid fuel ingredients. the refining industry has been confronted by the problem of how to utilize refinery gases more fully in these processes and of how to obtain therefrom the most valuable products.

As a meritorious answer to the above problem, there is herewith provided a process in which a boron fluoride with admixed water is employed as the catalyst.

The herein provided method of applying` the polymerization and alkylation treatments to selected hydrocarbon mixtures has distinct advantages over any one kind of treatment applied to l all the reactive hydrocarbons involved in the polymerization is selectively imposed on C4 olefins i in the presence of C4 paramns to form one main portion of the desired final fuel product and a complementary alkylation treatment is selectively imposed on C2 and C: oleiins together with C4 paramns emciently recovered from the polymerization to yield ingredients best suited as the other main portion of the desired final fuel y product.

Polymerization and aikylation reactions as applied to mixtures of oleiinic and paraflnic hydrocarbons are complicated and result in the formation of many types of hydrocarbons. Each of these reactions is considerably influenced by the kinds of hydrocarbons entering into the reaction as well as by the catalyst and conditions. Thus, any attempt to utilize a polymerization reaction along with an alkylation reaction offers difficulties in ascertaining the most suitable conditions, the manner of securing the reactants, and the manner of using the products and by-products of the reactions to the fullest advantage.

For the present purposes, it has been found that a preferred polymerization treatment is one in which normal butenes and iso-butene present in a C4 fraction are copolymerized or interpolymerized by a hot sulfuric acid catalyst to favor the formation of iso-octene isomers boiling above 225 F. (The terms "copolymerization and interpolymerization as used in this specification refer to the formation of polymers by the interaction of unlike isomeric molecules. as in the case under discussion, and copolymers and interpolymers" refer to the product formed by such process.) By hydrogenating the hydrocarbons recovered from the polymerization, then fraction- Fil ating out the normally liquid products, an isobutane-butane mixture is obtained in satisfactory condition for an alkylation reaction of the isobutano with thelower olefins, especially ethylene,

to secure a good yield of the desired alkylate. The alkyiation treatment found most satisfactory for bringing about the reaction ofthe lower olens-with the isobutane is preferably one wherein present process and over combined types of treatments that fail to'make the important discrimi- -nation 'in the substances treated or fail to apply conditions of reaction essential in obtaining the desired intermediate and final products. A complete understanding of the present invention will be obtained from the following description of a plant operation with reference to the accompanying drawing. In the drawing, the procedure is illustrated by a schematic flow plan including elevational views of apparatus units involved. The drawing is not intended to be in any accurate or relative scale, nor to contain all details of conventional refinery equipment which may be utilized.

Refinery gases, such as normally gaseous hydrocarbons from a cracking unit stabilizer, in-

pylene, butylenes, isobutane. and other homolo-l gous olefins and paralns having2 to 4 carbon atoms, may be supplied to the system thru feed i inlet i for introduction into the base of the fractionator 2, or similar device, in order to separate a. fractional condensate of 'Ci hydrocarbons and a fractional condensate of C2 and Ca hydrocarbons. The C4 fraction preferably should be composed substantially of normal and isomeric butanes and butenes. This cut may be removed from the fractionator by line 3 to b e conducted by a pump t thru heat exchanger 5 to a polymerization reactor 6.

Narrow out fractions containingk `Ca and Ca olens and parafiins may be withdrawn from the fractionator 2 in one or more side streams by lines l and 1' to be conducted via line 8 by a pump Q thru cooler lli to an alkylation reactor .i l. To reduce the C3 olefin concentration in the mixture sent to the reactor ll, a portion of the side stream 1' may be eliminated thru line i2.

Gaseous'substances lower boiling than ethylene, e. g., methane and hydrogen, may be expelled from the fractionator 2thru1ine I3 to be used for product gaseous hydrocarbons from cracking or representative sample of a feed to the primary fractionator 2 has the following approximate analysis:

Gaseous hydrocarbons recycled in the system are preferably subjected to pyrolytic or catalytic cracking and/or dehydrogenation before being introduced into the primary fractionator. To effect `such treatments, recycled gases from line I5 with any desired admixture of natural or refinery gases from line I8 are forced by pump I9 *hru heating` coll I6. For pyrolytic cracking, the hydrocarbon gases are heated to a temperature of about 1100 F. or higher. The heated gases may be discharged from the heating coil by line 20 thru cooler 2l into the base of fractionator 2. Alternatively, normally gaseous hydrocarbons fed into coil i6 may be heated to a somewhat lower temperature of about 950 F. to about 1050 F., and then be discharged thru line 22 into a reactor I'I wherein the heated hydrocarbons may be contacted with a catalyst that promotes cracking or dehydrogenation, for example, an acid-treated clay, active alumina, active silica, a dilcultly reducible oxide of metals like chromium. molybdenum, tungsten, magnesium, zinc, or mixed catalytic substances of these types.' From the reactor Il, the hydrocarbon products are Vpassed by line 23 thru cooler 2l into the fractionator 2. Thus, the hydrocarbons may be treated under.

suitable dehydrogenating conditions and also isomerizng conditions to favor the formation of olens and branched chain aliphatic hydrocarbons. Hydrocarbons heavier than the C4 parafns and olens that enter fractionator 2 may be withdrawn therefrom by the bottom outlet line 24.` The C4 fraction, sent from the fractionator` 2 to a polymerizationreactor 6, is treated therein under conditions appropriate for polymerizing and copolymerizing the ,C4 olens but avoiding their reaction with`any'of the C4 paraillns, so that the C4 oleilns are made to form a series of isomeric octenes boiling predominantly above 225 F. Correct conditions of treatment for this purpose are the following: The titratable sulfuric acid strength ranges from about 50% to 75% by weight, preferably from 60% to 70%. The temperature of polymerization is in the range of about 125 F. to 250 F., preferably from 160 F. to 175 F. The hydrocarbons are maintained in the liquefied state under pressures ranging from about 150 to 450 lbs/sq. in. gauge; and the reaction time is about2 to 30 minutes, preferably about to 20 minutes.

To reach the desired extent of polymerization, the reaction mixture may be passed thru one or a number of reaction zones underl operating conditions described.

The polymerization reaction mixture is withdrawn from reactor 6 by way of line 23 to separator 21 wherein separation is eected between the treated hydrocarbons and acid catalyst so -ihat spent acid catalyst may be removed thru line A portion of spent acid catalyst may be returned to the polymerization reactor by way of .pump 29 and line ill),` while Vanother portion of the spent catalyst may be withdrawn from the system thru line 3|. Fresh acid catalyst is sent to the reactor from line 30'. With the recycled spent catalyst may also be recycled some of the unseparated reaction mixture emulsion.

The treated hydrocarbon product separated from the acid catalyst in separator 21 is passed by line 32 to a washing unit 33, into which a dilute caustic washing agent is introduced by line 34 and the spent washing agent is removed thru line 35. The washing with dilute caustic may be followed by water washing and drying, if needed, to completely remove all treating agents from the hydrocarbons.

Following washing and any drying required, r

the hydrocarbon polymerization products are passed by .pump 36 in line 31 thru a preheater 38 into the catalytic hydrogenation reactor 39 with a suitable amount of admixed hydrogen from separator 43, the gas being removed thru outlet line 44.

Suitable conditions for the hydrogenatlon are as follows: lie in the rangeof about 200 F. to 650-F. A superatmospheric pressure, preferably ranging upwardly from about 200 lbs./sq. in. to about 3,000 lbs/sq. in. gauge is employed. The time of reaction may vary from about 10 to 60 minutes or more. Suitable catalysts for the hydrogenation are finely divided metals, such as nickel or copper, alone or supported on carriers, such as pumice, and certain metal oxides and metal suldes, notably oxides and suldes of zinc, magnesium, thorium, chromium, molybdenum, and of similar metals may be employed in place of the elemental metals. The metal oxides and sul `rides may be used in a. mixed catalyst, preferably immune to sulfur poisoning. In employing the free metal catalysts, the hydrocarbons and hydrogenating gas should be properly free of sulfur,

Aseparator 43 thru line 45 into a fractionating unit 46 equipped at the base with a rebolllng heat exchanger 41 and a bottom drain 48. This fractionating unit may be constructed in the form of a tower with a sufllcient volume and a simi-- cient number of fractionating plates for making a precise fractionation of the hydrocarbons. It is preferred to collect an intermediate fractional distillate boiling in the range of about 225 F. to 245 F. on intermediate plates in the fractionating column and to collect a separate lighter fraction boiling from about 200 F. to 225 F. on upper plates in the column. Uncondensedl vapors may be passed overhead from the fractionating column thru line 48 into a reflux analyzer 50, whence reflux maybe returned by line 5I to the upper part of the fractionating column. Uncondensed gases are forwarded by line 52 thru pump 53 to be commingled with lower molecular weight olens separated in the primary fractionating unit 2 for reaction in the alkylating unit Il.

Temperatures of the hvdrogenationv aaeaeos The intermediate fractional distillate and lighter distillate fractions referred to are withdrawn as side streams from' the fractlonator 06 by lines @C and 58 respectively. v

In the alkylation unit il` the mixture of Ci parains andlighter olens properly proportioned are made to react in the presence of a catalyst which fosters alkylation of ethylene with isobutane under suitable` conditions to form agood yield of alkylate hydrocarbons boiling between 125 F. and 280 F., and containing a substantial proportion boiling within the boiling range of 130 F. to 138 F. This isaccomplished preferably in the following manner: The oleilns present in the reaction mixture should be as free as possible of butenes or higher olens and should contain ethylene in a major proportion. The

ratio of ethylene to propylene should lbe 1.5:1 at a minimum, and preferably 4:1 or higher. The C4 paralns should be proportioned to the oleiins to have an isobutane to olefin ratio of at I least 2:1 and preferably 3:1 and higher. The preferred catalyst is a hydrated boron fluoride or boron fluoride mixed with water containing a major proportion oi the boron uoride and preierably at least about 70% thereof. The reaction is carried out at moderate temperatures of the order of about 60 F. to 80 F. and under a superatmospheric pressure of the order of 100 to 250 lbs/sq. in. gauge to maintain the hydrocarbons in liquid phase. The catalyst is fed in with the hydrocarbons to give a catalyst to hydrocarbon ratio of about 1:1 or 1:2. With average to good operating conditions, the yield of alkylate amounts to about 170% to 230% based on the weight of the oleins. Y

The catalyst may lLsupplied to the reactor Il from the feed inlet 5 and a substantial amount of recycle catalyst may be admixed from line 5l with the fresh catalyst.. To reach the desired extent of alkylation, one or several reaction units may be' employed, but for the sake a single reactor is illustrated.

From the reactor Il, the reaction mixture is passed by line 50 to separator 59, wherein the hydrocarbon oil product is separated from the spent catalyst by settling. Spent catalyst is withdrawn from the separator thru line 60, from which a portion of the spent catalyst may be discharged thru line 6 I, and another portion may be recycled to the reactor by pump 62 -thru line 51.

The separated alkylatlon Yproduct is removed from the separator thru line 63 into a neutralizer Sal-into which is led from line 85 a dilute neutralizing alkaline wash agent for removal of any acid or catalyst left in the alkylation product. The

l spent washing agent is removed from the neutralizar by drain pipe 66. The washed alkylate is removed from the neutralizer by line 6l and pump 68 to a fractionating ferred intermediate hydrogenated copolymer 'of simplicity,

unit @Si ior the desired separation of alkylation products.

The iractionating unit S9 may be in the form oi a iractionating column provided with a suitable number of plates, with reiluxing means it, and reboiling means ll. By equipping the fractionator with a suiilcient number of plates and maintaining a sulciently high reiux ratio, a. very satisfactory fractionation is obtained to recover the precise alkylate products which are xnost suitable for combination with higher boiling hydrogenated copolymer products described. a typical fractionation of' the total alkylate obn the `:following cuts:

Bo Vol. per Cut number range, F. cent yield The most desirable cut for the mulating superior aviation fuels the one'boillng in the range of about 130 F. to about 138 F., indicated by the asterisk, hence the quality of the alkylate product maybe judged by the proportion of this cut yielded; This preferred intermediate boiling range alkylate product may be collected on an intermediate plate in the fractionating column 69 to be withdrawn as a side stream thru line l2, so that it may be combined in a desired proportion with the prefraction boiling mostly in the range of 225 F. to 245 F., and which is withdrawn as a side streamjrom the fractionating unit i6 thru line dit.

Uncondensed gas led overhead from the fractionator S9 thru line 13 into reuxing means 'l0 is subjected to sufficient cooling and condensation to permit mostly unconverted Cz and Cs hydrocarbons to remain in the gas phase. This residual gas may be sent by lines 14 and l5 to line l5, then to the heating coil I6, and any excess of this gas may be removed from the system thru line t8. Reflux is returned from the reuxing means l0 by line l1 to thel upper part of the fractionator 89. In the upper part of the fractionating column a cut may be collected of butanes and removed byline 18 for use as a .charging stock in an isomerization to prepare A. C4 cut obtained by fractionating a normallygaseous hydrocarbon feed contained approximately 17.6% of isobutylene, 23.6% normal butane, 29.4% isobutane, and 29.4% normal butylenes. This cut was subjected to polymerization at F. under a pressure of 175 lbs/sq. in. with 69% sulfuric acid. 20 volumes of` recycle acid wereused to one volume of fresh feed. The contact time was about l5 minutes in the polymerization reactor. The polymer yield obtained was li0 volumes per cent on the basis of the lsobutylene. Following separation of the acid catalyst and neutralization of the treated hydrocarbons. the hydrocarbons were subjected tohydrogenation at 600 F. under a pressure of 3,000 lbs/sq. in. with a contact catalyst containing a mixture of zinc oxide, magnesium oxide, and molybdic oxide partially sulfurized. After the purpose of foris particularly separationof the excess hydrogenating gas, the

hydrogenated hydrocarbons were fractionated in a distillation column wherein two cuts were made. The lighter of these cuts boiled substantially in the range of about 210 F. to 220 F., and the heavierboiled fin the range of about 225 F. to 250 F. Each of these cuts was removed in a separate side stream from a distillation column. The gas removed overhead from the distillation column contained no substantial amount of butenes but was composed substantially of normal and isobutane..

` The normal butane-isobutane hydrocarbon mixture obtained by separation from the hydrogenated copolymerization products described was added to an ethylene cut fractionated from the initial feed. This ethylene cut contained four mols of ethylene to one of propylene, and a suilicient amount ofthe butanes substantially free of-butenes was added to make the isobutane to olen ratio amount to about 3:1. The resulting mixture was treated in an alkylation unit under 200 lbs/sq. in. pressure at a temperature of 70 F. with a catalyst composed of 78% boron lfluoride and 22% water to obtain an alkylate which after puriication and upon distillation was found to have the following distillation characteristics:

. V1"". Initial boiling point 12'? 10% distilled off at 142 50% distilled off at 161 90% distilled off at 226 Final boiling point 268 In the distillation of the alkylation product, a reiiux ratio of about 10:1 was used in a distillation column containing 10 plates so as to segregate with good precision a cut having a boiling boiling substantially within the range of 225 F.

to 245 F. in ratios of 10 to 80, 30 to 70, and 50 to 50 per cent by volume, fuel compositions were obtained which gave amazingly excellent performance in a supercharged aviation engine. These fuel compositions, blended with 3 cc. of tetraethyl lead per gallon, were found to give a knock-free performance equivalent to that of isooctane (100 A. S. T. M. octane rating) blended g with as much as 6 cc. of tetraethyl lead per gallon under indicated mean eective pressures ranging upwardly from 233 lbs/sq. in.

It was thus determined that the operations of hot acid polymerization followed by hydrogenation on a C4 cut gave an optimum yield of the desired high boiling isoparamns and at the same time furnished very expedently the required sat urated C4 hydrocarbons which made the alkylation of ethylene and propylene work out satisfactorily. Also, it was thus determined that the major products derived from the polymerization in combination with the predominant alkylation products formed a superior aviation fuel. Thus,-

the present process proved satisfactory for eliminating diillculties of separating hydrocarbons from refinery gas mixtures and for obtaining a high overall eiliciency in the conversion of the various normally gaseous hydrocarbons ordinarily present in refinery gases to the most vaiuable liquid fuels. f' The present invention is not to be limited by any theory on reactions involved nor by any par ticular examples given for the Purpose of illustration. Any modifications coming wlthinrthe -spirit of the invention are intended to be included within the scope thereof.

Iclaim:

1. In a process for preparing a high anti-knock aviation fuel from normally gaseous hydrocarbons, the steps of copolymerizing the oleflnsin a butylene-butane cut by a hot sulfuric acidcatalyst to form iso-octenes boiling predominantly above 225 F., hydrcgenatingthe. hydrocarbons from the polymerization treatment, fractionat-j ing the resulting hydrogenated hydrocarbosto separate therefrom saturated normally gaseous hydrocarbons constituted of isobutane and btane and a liquid isoparatlinic fraction boilin! predominantly above about 225 F., alkylating olens in a C: to C: cut with said separated isobutane-butane fraction in the presence of a boron fluoride-.water catalyst under suitable conditions to form an alkylate boiling mainly above 130 F., and combining a4 portion of 'said alkylate with said isoparafllnic fraction boiling above 225 F.

2. A process for preparing a high anti-knock aviation fuel, which comprises converting C4- oleilns in a mixture with normal butane and isobutane to form iso-octenes boiling mainly above 225 F. by polymerization in the presence of a hot sulfuric aid catalyst, separating resulting polymers and residual unreacted normally gaseous-Ci hydrocarbons from-the catalyst, hydrogenating all of -said separated hydrocarbons, adding said normally gaseous hydrocarbons substantially free of C4 olellns, after separation from thetotal products of the hydrogenation step, to ethylene undergoing alkylation with isobutane, and-combining resulting alkylated ethylene with hydrogenated iso-octenes boiling mainly above-225 Fl" ,recovered from the hydrogenated polymers.

3. A process for preparing an aviation gasoline, v-

whlch comprises copolymerizing liqueed butenes in the presence of butanes with a hot sulfuric acid catalyst atA about F. to 250'F.,jhydro genating hydrocarbons separated from. said catalyst following the copolymer-ization; fractionating the hydrogenated hydrocarbons to recover a liquid isoparamnic fraction boiling mainly in the range of 225 F. to 245 F. and residualy butanes, alkylating ethylene with isobutane in said residual butanes using boron iiuoride and water "as the catalyst at about 60 F. to 80 F., and comi blning with said liquid isoparafiinic fraction a resulting alkylate boiling mainly in the range of l F. to 138 F.

4. In a process for preparing a high anti-knock aviation fuel from normally gaseous hydrocarbons, the steps of submitting a mixture of C4 olenns and paraillns to a hot sulfuric acid polymerization treatment to form iso-octenes boiling predominantly above 225 F., hydrogenating the hydrocarbons from the polymerizationv treatment. fractionating the resulting hydrogenated hydrocarbons to separate therefrom'normally gaseous hydrocarbons consisting essentially of rl-butan4 and isobutane and a liquid isoparaillnic fraction boiling predominantly above 225 F., alkylating C: to Ca olens with said separated butane-iso-..r butane fraction, and combining thealkylate thus formed with said isoparailinic fraction boiling predominantly above 225 F. 

